EP0250671B1 - Vorrichtung zur Abgabe von Flüssigkeitsdosen - Google Patents

Vorrichtung zur Abgabe von Flüssigkeitsdosen Download PDF

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Publication number
EP0250671B1
EP0250671B1 EP86305189A EP86305189A EP0250671B1 EP 0250671 B1 EP0250671 B1 EP 0250671B1 EP 86305189 A EP86305189 A EP 86305189A EP 86305189 A EP86305189 A EP 86305189A EP 0250671 B1 EP0250671 B1 EP 0250671B1
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EP
European Patent Office
Prior art keywords
liquid
point
lens
light
pipette
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86305189A
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English (en)
French (fr)
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EP0250671A1 (de
Inventor
Hidechika Hayashi
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Tosoh Corp
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Tosoh Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU59451/86A priority Critical patent/AU585033B2/en
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to EP86305189A priority patent/EP0250671B1/de
Priority to DE8686305189Q priority patent/DE3683493D1/de
Publication of EP0250671A1 publication Critical patent/EP0250671A1/de
Priority to US07/338,508 priority patent/US4944922A/en
Application granted granted Critical
Publication of EP0250671B1 publication Critical patent/EP0250671B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1009Characterised by arrangements for controlling the aspiration or dispense of liquids
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1009Characterised by arrangements for controlling the aspiration or dispense of liquids
    • G01N2035/1025Fluid level sensing
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N2035/1027General features of the devices
    • G01N2035/103General features of the devices using disposable tips
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1081Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices characterised by the means for relatively moving the transfer device and the containers in an horizontal plane
    • G01N35/1083Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices characterised by the means for relatively moving the transfer device and the containers in an horizontal plane with one horizontal degree of freedom
    • G01N2035/1086Cylindrical, e.g. variable angle
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00Chemistry: analytical and immunological testing
    • Y10T436/11Automated chemical analysis
    • Y10T436/117497Automated chemical analysis with a continuously flowing sample or carrier stream
    • Y10T436/118339Automated chemical analysis with a continuously flowing sample or carrier stream with formation of a segmented stream

Definitions

  • the present invention is directed to a quantitative dispenser for small amounts of liquid samples or reagents and more specifically to a quantitative dispenser using an optical sensing device for controlling the amount of liquid to be dispensed.
  • the negative pressure can be strictly controlled when the pipette is inserted into a sample vessel.
  • the depth to which the nozzle of the pipette is immersed in the sample solution is likely to vary depending upon the size of the sample. The variation may give rise to an error in the quantitative dispensing which cannot be ignored.
  • the same problem also arises when the surface of the sample solution is concave due to the formation of a meniscus or the vessel itself is in a slanted position and its diameter is small.
  • Electrodes to sense the level of the liquid surface in a dispensing device.
  • electrode types of detector involve contamination and non-contact types of optical detector generally are not sufficiently precise, some having tolerances of several millimetres, and therefore cannot accurately operate with turbid solutions or slanted surfaces.
  • an error of several millimetres in immersion may introduce, for example, up to ten percent of dispersion when 5 ⁇ l of solution is taken with a pipette of 200 ⁇ l capacity.
  • DE-A-3113248 does not utilize a lens system but instead uses bundles of photoconductive fibres which may be in an ordered array or a random array.
  • the invention in this document is concerned with detecting the surface of a liquid which is liable to movement and is not as smooth as glass. It is not concerned with the problem of a tilted or curved surface.
  • the structure shown has no means for gathering in and focussing light rays onto a point sensor so as to concentrate them and enable the point of maximum intensity to be detected even if the surface is inclined or curved.
  • CH-A-499096 has only a single lens system and has no means for gathering in rays reflected from an inclined or curved surface. In addition it does not focus the reflected rays onto a receiver but rather collects only a minor portion of the reflected rays, namely those on the axis of the single lens.
  • the device of this document is not concerned with detecting the actual level of the liquid (so as to enable a nozzle to be immersed in the liquid to enable an accurate sample to be taken) but rather with detecting when a given level has been reached so that a foam destroying agent can be injected into the liquid once that level has been reached.
  • CH 499096 uses a face light source rather than a point light source. Accordingly the image of the light source does not condense or focus to a definite point but gives an image similar to the light source.
  • the lens which controls the irradiation of the surface to be detected is supplied with a parallel beam of light rather than from a point source.
  • the lens on which diffuse rays impinge does not focus them onto a point detector. It is an object of the present invention to provide a new and improved quantitative dispenser for a liquid which is capable of dispensing a precisely controlled amount of liquid when a minute amount of liquid is to be taken up.
  • a quantitative dispenser for a liquid comprising a pipette having a downwardly directed nozzle adapted to pick up and deliver a predetermined quantity of the liquid, means for moving the pipette downwards to immerse the lower end of the nozzle in the liquid, a liquid level sensor for determining the position of the liquid surface and a control system for determining the stopping point for the downward movement of the pipette, characterised in that the liquid level sensor comprises a lens system, a point light source arranged to direct a beam of light through the lens system onto the surface of the liquid, and a point light sensor for receiving light reflected from the surface of the liquid through the lens system, the control system being operatively connected to the point light sensor and to the means for moving the pipette for stopping the downward movement of the pipette at a position corresponding to that where a maximum intensity of the reflected light is detected by the point light sensor, the lens system comprising first and second lens placed side by side, the first lens being supplied with light from the
  • the dispenser includes means connecting the pipette and the sensor together for simultaneous downward movement towards the liquid.
  • the sensor may be mounted separately from the pipette and separate means are provided for moving the sensor and the pipette independently.
  • the mechanism for moving the pipette downwardly may comprise a support frame on which the indication device of the pipette is supported for movement in the vertical direction and means for moving the frame up and down such as a pulse motor operating through an intermediate cam mechanism.
  • the spot type reflection sensor to be used in the present invention may be comprised of a light emitting portion and a light receiving portion in which the light from the light source and reflected light are transmitted through a convergent optical element such as a convex lens.
  • the senor includes a housing in which the lens system, the photosensor, and the light source are located.
  • the portions may be either assembled in a unitary body or arranged separately in appropriate positions relative to each other.
  • the maximum intensity point of the reflected light detected by the reflection type sensor can be detected by converting the reflected light into an electrical signal and by detecting the high peak of the electrical signal.
  • the maximum intensity of the incoming reflected light occurs when the surface of the liquid coincides with the focus point of the light irrespective of a slanted surface or the turbidity of the liquid.
  • the stop point of the downwardly moving pipette as determined by the maximum intensity makes it possible to control precisely the depth to which the nozzle of the pipette is immersed in the liquid.
  • the present invention is suitable to those devices for analysis and measurement in which the quantitative dispensing of 1000 ⁇ l or less of a liquid is required. More particularly the dispenser according to the present invention is suitable in carrying out estimations in immunological and biochemical reactions where a very small amount of a liquid, of the order of 100 ⁇ l or less, is quantitatively dispensed.
  • the liquid dispensed may be a sample or a reagent.
  • the mechanism for lowering the sensor to approach the surface may be installed on the support frame supporting the pipette lowering mechanism or installed on a separate support frame independently from the pipette supporting frame. It is preferred that the point at which the sensor detects the liquid surface is horizontally as close as possible to the point where the lower end of the nozzle is partially immersed in the liquid to obtain a high degree of precision in the dispensing of the liquid.
  • a method for quantitatively dispensing a liquid in which a pipette having a nozzle is moved downwards to immerse the lower end of the nozzle in the liquid, the downward movement is stopped by position sensor and a control system, the liquid sample is taken up, the pipette is withdrawn, and the sample is dispensed, characterised in that the downward movement is stopped by directing a beam of light on to the liquid surface via a lens system, detecting the reflected light from the surface via the lens system with a photosensor, and stopping the downward movement of the pipette at a position corresponding to that where a maximum intensity of the reflected light is detected by the photosensor.
  • the position sensor and the pipette are moved downwards simultaneously.
  • the sensor is moved downwards, the position of maximum intensity of reflected light is recorded in a memory, and the pipette is subsequently lowered to the desired position, in dependence upon the position recorded in the memory.
  • the quantitative dispensing of a minute volume of liquid can be performed with an extremely high degree of precision.
  • various quantitative and qualitative analyses can be accurately and precisely controlled. It will be clear that a device according to the present invention can be applied to a number of automatic analytical systems and analysers.
  • the quantitative liquid dispenser as shown in Figure 1 comprises of a pipette 3 having a disposable tip 4 which is adapted to be moved into and out of a liquid sample contained in a sample vessel 1.
  • the pipette 3 is carried by a supporting rod or frame 6 which in turn is moved vertically by means of a drive mechanism 5 including a pulse motor under the control of a drive control circuit 9.
  • a spot type reflection sensor 10 is also firmly supported by the support rod or frame 6 for movement with the pipette.
  • the sensor 10 is located slightly higher than the lower end of the disposable tip 4 and an electrical signal from the sensor 10 is supplied to the control circuit 9 for controlling the drive mechanism 5.
  • the sensor 10 can be constructed, for example with an optical reflective sensor HEDS-1000 (Yokokawa Hewlett Packard Corp).
  • HEDS-1000 Yokokawa Hewlett Packard Corp
  • Such a spot type reflection sensor 10 emits light to the surface of the liquid 2 in the sample vessel 1 in which the lower end of the nozzle tube 4 is to be immersed and receives light reflected from the surface of the liquid.
  • the intensity of the reflected light reaches a maximum when the sensor 10 reaches a point above the surface equal to the focal distance of the lens within the detector, the focal distance being preset by selecting an appropriate convex lens such as that shown in Figure 4(b).
  • the plot diagram of several light intensity curves shown in Figure 2(a) illustrates the relationship of the light intensity relative to the distance 1 of the detector above the surface of the liquid.
  • the distance l1 from the surface of the liquid where the maximum intensity is obtained is constant as shown in Figures 2(a) regardless of the reflectivity of the liquid surface or the degree of concavity or slanting of the surface.
  • the depth of immersion of the nozzle tip into the liquid can be controlled with a high degree of accuracy.
  • the maximum intensity of the light can be detected by using a high-peak detecting circuit such as that shown in Figure 5 so that the downward movement of the pipette is stopped when the maximum value is detected or when the pipette moves a very short distance past the point of maximum intensity.
  • Figure 2(b) shows three representative positions of a light detector relative to a flat liquid surface with respect to three different portions of a light intensity curve such as that shown in Figure 2(a).
  • the focal point of the lens in the middle position is coincident with the surface of the liquid and the light intensity is at a maximum.
  • Figure 2(c) is similar but in this case the surface of the liquid is concave or inclined.
  • the overall intensity of the reflected light will be less in such a situation than with a flat surface as in Figure 2(b) but the light intensity will still be at a maximum when the focal point of the lens is coincident with the surface of the liquid.
  • the maximum or peak value of the light intensity is expressed as 100, the light intensity detected with 0.2 mm deviation from the focal length representing the maximum or peak value may be lowered about ten percent.
  • Figure 3 shows one embodiment of an apparatus suitable for carrying out the present invention which corresponds to the schematic arrangement shown in Figure 1.
  • the numerical references 1, 3, 4, 8 and 10 represent the same elements as shown in Figure 1.
  • a rotating shaft 5b is rotated by means of a pulse motor 5a to rotate a cam 5c by an amount corresponding to the amount of rotation of the pulse motor so that a frame 11 supporting the pipette 3 is moved downwards.
  • the disposable nozzle 4 detachably connected to the lower end of the pipette 3 is moved downwards by a corresponding amount and enters the liquid within the sample vessel.
  • the point at which the downwardly moving nozzle stops is determined by detecting the maximum value of the intensity of the reflected light by the sensor 10 which is mounted on the same support frame 11 as the pipette 3.
  • the detector 10 is connected to the detecting circuit and a source of power by means of a cable 14.
  • the support frame 11 is movable horizontally along guide rods 13 carried by a main frame 12 so as to allow the pipette to be moved selectively between various vessels and reaction chambers.
  • the support frame 11 may be moved along the guide rods 13 by any suitable means which have not been shown since such means are conventional in the art.
  • the photosensor 10 is shown in detail in Figure 4(a) and includes an LED light source 31 and a photodiode 32 mounted along side.
  • the light from the LED light source is projected outwardly of the glass window 33 through the convex lens 34 whose focal point is at 35.
  • the light reflected from the liquid surface passes through the convex lens 36 and enters the photodiode 32.
  • the signal input and output of the sensor 10 are connected to the drive control mechanism 9 as shown in Figure 1 through the cable 14 so that the maximum value of the intensity of the light incident on the photodiode is detected.
  • the convex lens element shown in Figure 4(b) is prepared by moulding a plastics material as one body with a skirt portion and a collar portion in such a shape as if two convex lenses are combined.
  • Figure 5 shows a block circuit diagram for the detection of the maximum intensity of the incident light in which an oscillator 15 supplies a signal to the detector 10 to activate the LED light source 31.
  • the signal from the photodiode 32 is passed through an amplifier 16, a wave detector 17 and an A/D converter 18 prior to being supplied to a microcomputer 19.
  • a suitable high peak detector can be constructed using the above components by a person having ordinary skill in the electrical arts.
  • Figure 6 is a flow chart showing the operational sequence for the embodiments described above.
  • the support frame 11 moves horizontally as described above the operational sequence is limited to the up and down movement of the pipette which is carried by the support frame 11.
  • the sampling head moves downwards and a light signal is supplied by the photosensor as the light from the photodiode is reflected from the surface of the liquid below the sampling head.
  • the input value changes from an increase to a decrease the downward movement of the sampling head is stopped, a sample is withdrawn from the liquid reservoir and the sampling head subsequently rises to complete the operational cycle.
  • the focal length of the sensor 10 in this embodiment is 4.3 mm, and the distance from the lower end of the sensor to the lower end of the nozzle tip is 7.3 mm.
  • the nozzle and sensor are fixed to the same control mechanism as shown in Figures 1 and 3.
  • FIG 7 shows a further embodiment of the present invention in which, the pipette 3 and the sensor 10 are mounted separately from each other on separate support mechanisms.
  • the detector 10 is carried by a supporting frame 21 which is mounted on a mechanism 22 for moving the frame 21 up and down.
  • the pipette 3 is mounted for movement by means of a mechanism similar to that described above with respect to Figure 3 and the details of the movement will not be repeated.
  • a downward movement of the sensor is detected and when the maximum value of reflected light intensity is detected the pulse motor for moving the pipette is controlled to limit the immersion of the tip of the pipette in the liquid.
  • sample vessels are shown as being mounted in a rack 20 and suitable means may be provided for moving the pipette and detector and the rack relative to each other to align the pipette with different samples.
  • suitable means may be provided for moving the pipette and detector and the rack relative to each other to align the pipette with different samples.
  • the volume of sample in a particular sample vessel is measured and memorised in a memory in the control mechanism. Then, when that sample vessel comes below the nozzle, the position at which the nozzle is stopped is determined on the basis of the memorised sample volume measurement of the vessel.
  • Figure 8 is a flow chart showing the operational sequence of the device of Figure 7.
  • the photosensor 10 is moved down towards the liquid surface of a selected sample vessel in 0.5 mm steps.
  • the position of the sample surface is calculated and stored in a memory.
  • the sensor 10 then rises and is moved away from the selected sample, while the nozzle tip 4 is brought to the selected sample.
  • the nozzle tip 4 is lowered until its end is 3 mm below the sample surface, using the recorded position of the surface from the memory.
  • a sample is withdrawn by suction and the nozzle tip 4 is raised.
  • a liquid volume of 5 ⁇ l is picked up with the lower end of the nozzle tip being immersed to a depth of 3 mm below the surface of the liquid.
  • the dispersion with respect to the depth of immersion of the nozzle tip was 1 mm or less and with respect to the volume of liquid picked up was two percent or less.

Claims (4)

  1. Vorrichtung zur Abgabe von Flüssigkeitsdosen mit einer Pipette (3), die eine nach unten gerichtete Düse (4) aufweist, die geeignet ist, eine bestimmte Flüssigkeitsmenge aufzunehmen und abzugeben, eine Einrichtung zum Abwärtsbewegen der Pipette (3), so daß das untere Ende der Düse (4) in die Flüssigkeit getaucht wird, einem Flüssigkeitsspiegelsensor (10) zum Bestimmen der Position der Flüssigkeitsoberfläche und einem Steuersystem (9) zum Bestimmen der Stoppstelle für die nach unten gerichtete Bewegung der Pipette (3), dadurch gekennzeichnet, daß der Flüssigkeitsspiegelsensor (10) ein Linsensystem (34, 36), eine Lichtpunktquelle (31), die so angeordnet ist, daß ein Lichtstrahl durch das Linsensystem (34) auf die Flüssigkeitsoberfläche gerichtet wird, und einen Lichtpunktsensor (32) zum Empfangen von von der Flüssigkeitsoberfläche durch das Linsensystem (36) reflektiertem Licht aufweist, wobei das Steuersystem (9) wirksam mit dem Lichtpunktsensor (32) und der Einrichtung zum Bewegen der Pipette (3) verbunden ist, zum Anhalten der nach unten gerichteten Bewegung der Pipette (3) an einer Stelle, die der entspricht, an der eine maximale Intensität des reflektierten Lichts durch den Lichtpunktsensor (32) detektiert wird, wobei das Linsensystem eine erste und eine zweite nebeneinander angeordnete Linse aufweist, der ersten Linse Licht von der Lichtpunktquelle zugeführt wird und die zweite Linse Licht mit dem Lichtpunktsensor detektiert, die optischen Achsen der zwei Linsen zueinander schräg liegen und sich in einem Kreuzungspunkt treffen, der genannte Punkt mit dem Brennpunkt der ersten Linse und mit dem Brennpunkt der zweiten Linse zusammenfällt, wodurch Licht von der Lichtpunktquelle das von der Flüssigkeitsoberfläche reflektiert wird, durch den Lichtpunktsensor detektiert wird, wenn die Flüssigkeitsoberfläche in dem genannten Brennpunkt liegt.
  2. Abgabevorrichtung nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß der Sensor ein Gehäuse aufweist, in dem das Linsensystem (34, 36), der Lichtpunktsensor (32) und die Lichtpunktquelle (31) angeordnet sind.
  3. Abgabevorrichtung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Linsensystem ein einzelnes Linsenelement aufweist, das aus zwei Teil-Konvexlinsen (34, 36) gebildet wird.
  4. Verfahren zur Abgabe von Flüssigkeitsdosen, wobei eine Pipette (3) mit einer Düse (4) nach unten bewegt wird, so daß das untere Ende der Düse (4) in die Flüssigkeit getaucht wird, die nach unten gerichtete Bewegung mittels eines Flüssigkeitsspiegelsensors (10) und eines Steuersystems (9) gestoppt wird, die Flüssigkeitsprobe aufgenommen wird, die Pipette (3) herausgezogen wird, und die Probe abgegeben wird, dadurch gekennzeichnet, daß die nach unten gerichtete Bewegung gestoppt wird, indem ein Lichtstrahl von einer Lichtpunktquelle (31) über eine erste Linse (34) auf die Flüssigkeitsoberfläche gerichtet wird, das von der Oberfläche reflektierte Licht über eine zweite Linse (36), die das Licht auf einen Lichtpunktsensor (32) fokusiert, detektiert wird, wobei die erste und die zweite Linse nebeneinander angeordnet sind, die optischen Achsen der zwei Linsen zueinander schräg liegen und sich in einem Kreuzungspunkt treffen, der mit dem Brennpunkt der ersten Linse und dem Brennpunkt der zweiten Linse zusammenfällt, und die nach unten gerichtete Bewegung der Pipette (3) an einer Stelle stoppt, die der entspricht, an der der Kreuzungspunkt auf der Flüssigkeitsoberfläche angeordnet ist und eine maximale Intensität des reflektierten Lichts durch den Lichtpunktsensor (32) detektiert wird.
EP86305189A 1986-07-04 1986-07-04 Vorrichtung zur Abgabe von Flüssigkeitsdosen Expired - Lifetime EP0250671B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU59451/86A AU585033B2 (en) 1986-07-04 1986-07-01 Quantitative dispenser for a liquid
EP86305189A EP0250671B1 (de) 1986-07-04 1986-07-04 Vorrichtung zur Abgabe von Flüssigkeitsdosen
DE8686305189Q DE3683493D1 (de) 1986-07-04 1986-07-04 Vorrichtung zur abgabe von fluessigkeitsdosen.
US07/338,508 US4944922A (en) 1986-07-04 1989-04-14 Quantitative dispenser for a liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86305189A EP0250671B1 (de) 1986-07-04 1986-07-04 Vorrichtung zur Abgabe von Flüssigkeitsdosen

Publications (2)

Publication Number Publication Date
EP0250671A1 EP0250671A1 (de) 1988-01-07
EP0250671B1 true EP0250671B1 (de) 1992-01-15

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EP86305189A Expired - Lifetime EP0250671B1 (de) 1986-07-04 1986-07-04 Vorrichtung zur Abgabe von Flüssigkeitsdosen

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US (1) US4944922A (de)
EP (1) EP0250671B1 (de)
AU (1) AU585033B2 (de)
DE (1) DE3683493D1 (de)

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US5045286A (en) * 1988-02-25 1991-09-03 Olympus Optical Co., Ltd. Device for aspirating a fixed quantity of liquid
EP0488761A2 (de) * 1990-11-30 1992-06-03 Tosoh Corporation Vorrichtung zur quantitativen Entnahme von Flüssigkeitsproben
CH682847A5 (de) * 1991-12-12 1993-11-30 Hamilton Bonaduz Ag Verfahren und Vorrichtung zum Verdrängen einer heterogenen Mischung.
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AU5945186A (en) 1988-01-07
AU585033B2 (en) 1989-06-08
US4944922A (en) 1990-07-31
DE3683493D1 (de) 1992-02-27
EP0250671A1 (de) 1988-01-07

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